Crystal structures of uranyl complexes with isobutyrate and isovalerate anions

Savchenkov, Anton V.; Вологжанина, Анна В.; Дмитриенко, Артем О.; Zubavichus, Yan V.; Pushkin, D. V.; Сережкина, Л. Б.; Сережкин, В. Н.

doi:10.1039/c7dt04042c

Cited by 7 publications

(2 citation statements)

References 47 publications

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“…This distinct layer arrangement leads to a symmetry change as well as to subtle variations in the topology of the compounds. The latter can be illustrated with coordination sequences of the nodes, which are summarized in Table and detail the number of metal atoms (i.e., nodes for a simplified net) in the n th coordination sphere. − Both the first and second coordination spheres are the same for the polymorphs, and a subtle difference starts only with the third coordination sphere, where the orthorhombic polymorph has 42 metal atoms versus 41 atoms for the monoclinic polymorph.…”

Section: Resultsmentioning

confidence: 99%

Synthetic Strategies for the Synthesis of Ternary Uranium(IV) and Thorium(IV) Fluorides

2018

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A series of new U(IV) and Th(IV) fluorides, NaUF (1), NaUF (2), NaUF (3), KThF (4), NaThF (5), (HO)ThF (6), and (HO)UF (7), was obtained using hydrothermal and low-temperature flux methods. Mild hydrothermal reactions with uranyl acetate as a precursor yielded 1, 7, and the monoclinic polymorph of NaUF, whereas direct reactions between UF and NaF led to the formation of 2 and orthorhombic NaUF (3). This highlights an unexpected difference in reaction products when different starting uranium sources are used. All seven compounds were characterized by single-crystal X-ray diffraction, and their structures are compared on the basis of cation topology, revealing a close topological resemblance between fluorides on the basis of the layers observed in NaUF(HO). Phase-pure samples of 1, 2, and both polymorphs of NaUF were obtained, and their spectroscopic and magnetic properties were measured. The UV-vis data are dominated by the presence of U cations and agree well with the electronic transitions. Effective magnetic moments of the studied compounds were found to range from 3.08 to 3.59 μ.

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Section: Resultsmentioning

confidence: 99%

Synthetic Strategies for the Synthesis of Ternary Uranium(IV) and Thorium(IV) Fluorides

2018

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“…These differences are understood to arise from the nature of U(IV) and U(VI) cations. Whereas U(IV) adopts more spherical coordination geometries, the structural chemistry of U(VI) is dominated by the linear uranyl (U VI O 2 2+ ) moiety for which coordination is largely limited to the equatorial plane. , Hexavalent uranium chemistry is arguably the most well-developed of the actinides; a number of ligand sets have been explored ranging from simple monodentate and polydentate carboxylates to amines, sulfates, and phosphates, with both aromatic and aliphatic backbones. The wide diversity of carboxylate-based ligand sets, in particular, has allowed for a catalog of U(VI) structures to be isolated and characterized in the solid state. ,− …”

Section: Introductionmentioning

confidence: 99%

Synthesis, Characterization, and Solid-State Structural Chemistry of Uranium(IV) Aliphatic Dicarboxylates

Murray

Wacker

Bertke

et al. 2021

Crystal Growth & Design

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Examinations of uranium(IV) complexation by aliphatic dicarboxylates, ranging from the three-carbon malonate to the six-carbon adipate, yielded six novel phases. Single crystals of the compounds were prepared through either evaporation or solvent layering, and the structures were determined via single-crystal X-ray diffraction. The compounds were further characterized via IR and Raman spectroscopies. For the phases synthesized via solvent layering, correlations between the solution- and solid-state speciation were probed using UV–visible absorption spectroscopy. In the presence of malonate (MA), [U(MA)2(H2O)3] n (U-1a) was isolated. As the crystals were not suitable for structure determination, reactions of MA with thorium were pursued. These efforts yielded polymorphs, Th-1a and Th-1b; in both An-1a (An = Th, U) and Th-1b, the An(IV) metal centers are bridged via the MA ligands into 2D sheets. Upon increasing the length of the aliphatic backbone, monodentate and bridging bidentate binding modes are observed. Two distinct ligand-bridged extended networks that vary in metal ion nuclearity were observed for succinate (SA): [UCl2(SA)(H2O)2] n (U-2) and [U6O4(OH)4(SA)4(H2O)10]·4Cl·mH2O (U-3). Whereas U-2 consists of mononuclear U(IV) atoms that are bridged through the organic carboxylate into a 3D network, U-3 is built from hexanuclear U(IV)-hydroxo-oxo clusters that are further bridged into a 3D network. From glutarate (GA) ligand systems, two phases were isolated including [UCl2(HGA)2(H2O)2] n (U-4) that consists of ligand-bridged one-dimensional chains and [U2Cl6(HGA)2(H2O)2] n (U-5), which is built from chloride-bridged {U2Cl2} dimers that are further linked via GA into two-dimensional sheets. Finally, in the presence of adipate (AA), [U6O4(OH)4(AA)4(H2O)8]·4Cl·7(H2O) (U-6) is observed; the structure consists of hexameric [U6O4(OH)4]12+ clusters that are propagated into one-dimensional chains via the AA and uranium-bound water molecules that directly link adjacent clusters. Taken together, this work provides a systematic examination of the influence of the identity of the dicarboxylate backbones on actinide structural chemistry and highlights the role that the organic ligand plays in stabilizing unique tetravalent actinide structural units.

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Restricted Speciation and Supramolecular Assembly in the 5f Block

Carter

Surbella

Kalaj

et al. 2018

Chemistry A European J

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Hybrid materials bearing elements from the 5f block display a rich diversity of coordination geometries, connectivities, and assembly motifs. Exemplary in this regard have been uranyl coordination polymers, which feature a wide range of secondary building units resulting from hydrolysis and oligomerization of the [UO ] cation. An alternative approach to novel materials, however, suppresses hydrolysis and relies on non-covalent interactions (e.g. hydrogen or halogen bonding) to direct assembly of a more limited suite of species or building units. This may be achieved through the use of high-anion media to promote singular actinyl anions that are assembled with organic cations, or by way of functionalized chelating ligands that produce complexes suited for assembly through peripheral donor/acceptor sites. Presented in this Concept article is therefore an overview of our efforts in this arena. We highlight examples of each approach, share our thoughts regarding delineation of assembly criteria, and discuss the opportunities for exploring structure-property relationships in these systems.

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Crystal structures of uranyl complexes with isobutyrate and isovalerate anions

Cited by 7 publications

References 47 publications

Synthetic Strategies for the Synthesis of Ternary Uranium(IV) and Thorium(IV) Fluorides

Synthetic Strategies for the Synthesis of Ternary Uranium(IV) and Thorium(IV) Fluorides

Synthesis, Characterization, and Solid-State Structural Chemistry of Uranium(IV) Aliphatic Dicarboxylates

Restricted Speciation and Supramolecular Assembly in the 5f Block

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